LISTS OF ACCEPTABLE POLYMERS FOR USE IN FOOD PACKAGING APPLICATIONS

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Tables 1 to 12 list polymers that have been granted no objection status by the Food Packaging Materials & Incidental Additives Section of the Chemical Health Hazard Assessment Division (Food Directorate) for use in food packaging applications. The polymers are coded and categorized as shown in the following table.

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1 Food Packaging Materials Food Packaging Materials LISTS OF ACCEPTABLE POLYMERS FOR USE IN FOOD PACKAGING APPLICATIONS Tables 1 to 12 list polymers that have been granted no objection status by the Food Packaging Materials & Incidental Additives Section of the Chemical Health Hazard Assessment Division (Food Directorate) for use in food packaging applications. The polymers are coded and categorized as shown in the following table. POLYMER CATEGORIES Table No. Polymer Type Code 1 polyethylenes PE 2 polypropylenes PP 3 polystyrenes PS 4 polyvinyl chlorides PVC 5 ionomers I 6 polyethylene terephthalates PET 7 polyvinyl acetates PVAc 8 polycarbonates PC 9 polyamides PA 10 polyvinyl alcohols PVOH 11 polyvinylidene chlorides PVDC 12 Others O For polycarbonate at a glance, click here.
2 Food Packaging Materials Polycarbonate, or specifically polycarbonate of bisphenol A, is a clear plastic used to make shatterproof windows, lightweight eyeglass lenses, and such. General Electric makes this stuff and sells it as Lexan. Polycarbonate gets its name from the carbonate groups in its backbone chain. We call it polycarbonate of bisphenol A because it is made from bisphenol A and phosgene. This starts out with the reaction of bisphenol A with sodium hydroxide to get the sodium salt of bisphenol A. The sodium salt of bisphenol A is then reacted with phosgene, a right nasty compound which was a favorite chemical weapon in World War I, to produce the polycarbonate. What? You want the gritty details of the reaction? Then click here and you will not be disappointed. Another polymer used for unbreakable windows is poly(methyl methacrylate). Seeing Another Polycarbonate More Clearly
3 Food Packaging Materials Up until now, we've been talking about only one polycarbonate, polycarbonate of bisphenol A. But there's another polycarbonate out there, that some of us look at all the time. In fact, some of us, like me, never look at anything without the help of this polycarbonate. This is the polycarbonate that is used to make ultra-light eyeglass lenses. For people with really bad eyesight, like me, if the lenses were made out of glass, they would be so thick that they'd be too heavy to wear. I know. I used to have glass lenses. My glasses were so heavy that wearing them gave me a headache. But this new polycarbonate changed all that. Not only is it a lot lighter than glass, but it has a much higher refractive index. That means it bends light more than glass, so my glasses don't need to be nearly so thick. So what is this wonderful new polycarbonate? It's very different from polycarbonate of bisphenol A. We make it by starting with this monomer: You can see that it has two allyl groups on the ends. These allyl groups have carbon- carbon double bonds in them. This means they can polymerize by free radical vinyl polymerization. Of course, there are two allyl groups on each monomer. The two allyl groups will become parts of different polymer chains. In this way, all the chains will become tied together to form a crosslinked material that looks like this: As you can see, the carbonate-containing groups (shown in blue) for the crosslinks between the polymer chains (shown in red). This crosslinking is makes the material very
4 Food Packaging Materials strong, so it won't break nearly as easily as glass will. This is really important for kids' glasses! If only this stuff had been invented when I was a kid! There is a fundamental difference in the two types of polycarbonate described here that I should point out. Polycarbonate of bisphenol A is a thermoplastic. This means it can be molded when it is hot. But the polycarbonate used in eyeglasses is a thermoset. Thermosets do not melt, and they can't be remolded. They are used to make things that need to be really strong and heat resistant. For polyethylene at a glance, click here! Polyethylene is probably the polymer you see most in daily life. Polyethylene is the most popular plastic in the world. This is the polymer that makes grocery bags, shampoo bottles, children's toys, and even bullet proof vests . For such a versatile material, it has a very simple structure, the simplest of all commercial polymers. A molecule of polyethylene is nothing more than a long chain of carbon atoms, with two hydrogen atoms attached to each carbon atom. That's what the picture at the top of the page shows, but it might be easier to draw it like the picture below, only with the chain of carbon atoms being many thousands of atoms long: Sometimes it's a little more complicated. Sometimes some of the carbons, instead of having hydrogens attached to them, will have long chains of polyethylene attached to them. This is called branched, or low-density polyethylene, or LDPE. When there is no branching, it is called linear polyethylene, or HDPE . Linear polyethylene is much stronger
5 Food Packaging Materials than branched polyethylene, but branched polyethylene is cheaper and easier to make. Linear polyethylene is normally produced with molecular weights in the range of 200,000 to 500,000, but it can be made even higher. Polyethylene with molecular weights of three to six million is referred to as ultra-high molecular weight polyethylene, or UHMWPE. UHMWPE can be used to make fibers which are so strong they replaced Kevlar for use in bullet proof vests. Large sheets of it can be used instead of ice for skating rinks.
6 Food Packaging Materials Polyethylene is vinyl polymer, made from the monomer ethylene. Here's a model of the ethylene monomer. It looks like some sort of art nouveau teddy bear if you ask me. Branched polyethylene is often made by free radical vinyl polymerization. Linear polyethylene is made by a more complicated procedure called Ziegler-Natta polymerization. UHMWPE is made using metallocene catalysis polymerization. But Ziegler-Natta polymerization can be used to make LDPE, too. By copolymerizing ethylene monomer with a alkyl-branched comonomer such as one gets a copolymer which has short hydrocarbon branches. Copolymers like this are called linear low-density polyethylene, or LLDPE. BP produces LLDPE using a comonomer with the catchy name 4- methyl-1-pentene, and sells it under the trade name Innovex ¨. LLDPE is often used to make things like plastic films.
7 Food Packaging Materials For polypropylene at a glance, click here! Polypropylene is one of those rather versatile polymers out there. It serves double duty, both as a plastic and as a fiber. As a plastic it is used to make things like dishwasher-safe food containers. It can do this because it doesn't melt below 160 oC, or 320 oF. Polyethylene, a more common plastic, will anneal at around 100 oC, which means that polyethylene dishes will warp in the dishwasher. As a fiber, polypropylene is used to make indoor-outdoor carpeting, the kind that you always find around swimming pools and miniature golf courses. It works well for outdoor carpet because it is easy to make colored polypropylene, and because polypropylene doesn't absorb water, like nylon does. Structurally, it is a vinyl polymer, and is similar to polyethylene, only that on every other carbon atom in the backbone chain has a methyl group attached to it. Polypropylene can be made from the monomer propylene by Ziegler-Natta polymerization and by metallocene catalysis polymerization. This is what the monomer propylene really looks like: Wanna know more? Research is being conducted on using metallocene catalysis polymerization to synthesize polypropylene. Metallocene catalysis polymerization can do some pretty amazing things for polypropylene. Polypropylene can be made with different tacticities. Most
8 Food Packaging Materials polypropylene we use is isotactic. This means that all the methyl groups are on the same side of the chain, like this: But sometimes we use atactic polypropylene. Atactic means that the methyl groups are placed randomly on both sides of the chain like this: However, using special metallocene catalysts it is believed that we can make polymers which contain blocks of isotactic polypropylene and blocks of atactic polypropylene in the same polymer chain, as is shown in the picture: This polymer is rubbery, and makes a good elastomer. This is because the isotactic blocks will form crystals by themselves. But because the isotactic blocks are joined to the atactic blocks, each little hard clump of crystalline isotactic polypropylene will be tied together by soft rubbery tethers of atactic polypropylene, as you can see in the picture on the right. To be honest, atactic polypropylene would be rubbery without help from the isotactic blocks, but it wouldn't be very strong. The hard isotactic blocks hold the rubbery isotactic material together, to give the material more strength. Most kinds of rubber have to be crosslinked to give them strength, but not polypropylene elastomers. Elastomeric polypropylene, as this copolymer is called, is a kind of thermoplastic elastomer. However, until the research is completed, this type of polypropylene will not be commercially available. The polypropylene which you can buy off the shelf at the store today has about 50 - 60% crystallinity, but this is too much for it to behave as an elastomer.
9 Food Packaging Materials For poly(ethylene terepthalate) at a glance, click here! Polyesters are the polymers, in the form of fibers, that were used back in the seventies to make all that wonderful disco clothing, the kind you see being modeled on the right. But since then, the nations of the world have striven to develop more tasteful uses for polyesters , like those nifty shatterproof plastic bottles that hold your favorite refreshing beverages, like the blue bottle in the picture below. So you see, polyesters can be both plastics and fibers. Another place you find polyester is in balloons. Not the cheap ones that you use for water balloons, those are made of natural rubber. I'm talking about the fancy ones you get when you're in the hospital. These are made of a polyester film made by DuPont called Mylar. The balloons are made of a sandwich, composed of Mylar and aluminum foil. Materials like this, made of two kinds of material, are called composites. A special family of polyesters are polycarbonates. Polyesters have hydrocarbon backbones which contain ester linkages, hence the name. The structure in the picture is called poly(ethylene terephthalate), or PET for short, because it is made up of ethylene groups and terephthalate groups (duh!). I realize that terephthalate is not the kind of word most English-speaking mouths are used to saying, but with practice you should be able to say it with only a slight feeling of awkwardness when it rolls off your tongue. The ester groups in the polyester chain are polar, with the carbonyl oxygen atom having a somewhat negative charge and the carbonyl carbon atom having a somewhat positive charge. The positive and negative charges of different ester groups are attracted to each other. This allows the ester groups of nearby chains to line up with each other in crystal form, which is why they can form strong fibers.
10 Food Packaging Materials The inventor who first discovered how to make bottles from PET was Nathaniel Wyeth. He's the brother of Andrew Wyeth the famous painter. But others had tried before. Go read this story of someone who may have been the first person to try to make a shatterproof bottle. Now I'm sure everyone out there is just dying to have two questions answered. The first one is: Why can't you return plastic soft drink bottles to get a cool nickel per bottle like you could with the old glass bottles? And the second one which I'm positive everyone is wondering about is: How come peanut butter comes in neato shatterproof jars but jelly doesn't? These two riveting questions, as it turns out, have the same answer. The answer is that PET has too low a glass transition temperature, that is the temperature at which the PET becomes soft. Now reusing a soft drink bottle requires that the bottle be sterilized before it is used again. This means washing it at really high temperatures, temperatures too high for PET. Filling a jar with jelly is also carried out at high temperatures. Down at your local jelly factory, the stuff is shot into the jars hot, at temperatures which would cause PET to become soft. So PET is no good for jelly jars. PEN Saves the Day! There is a new kind of polyester that is just the thing needed for jelly jars and returnable bottles. It is poly(ethylene naphthalate), or PEN. PEN has a higher glass transition temperature than PET. That's the temperature at which a polymer gets soft. The glass transition temperature of PEN is high enough so that it can withstand the heat of both sterilizing bottle washing and hot strawberry jelly. PEN is so good at standing the heat that you don't even have to make the bottle entirely out of it. Just mixing some PEN in with the old PET gives a bottle that can take the heat a lot better than plain old PET. In the big plants where they make polyester, its normal to start off with a compound called dimethyl terephthalate. This is reacted with ethylene glycol is a reaction called transesterification. The result is bis-(2-hydroxyethyl)terephthalate and methanol. But if we heat the reaction to around 210 oC the methanol will boil away and we don't have to worry about it anymore.
11 Food Packaging Materials Then the bis-(2-hydroxyethyl)terephthalate is heated up to a balmy 270 oC, and it reacts to give the poly(ethylene terephtalate) and, oddly, ethylene glycol as a by product. Funny, we started off with ethylene glycol. If you want to know how all these reactions go down, click here. But in the laboratory, PET is made by other reactions. Terephthalic acid and ethylene glycol can polymerize to make PET when you heat them with an acid catalyst. It's possible to make PET from terephthoyl chloride and ethylene glycol. This reaction is easier, but terephthoyl chloride is more expensive than terephthalic acid, and it's a lot more dangerous.
12 Food Packaging Materials There are two more polyesters on the market that are related to PET. There is poly(butylene terephthalate) (PBT) and poly(trimethylene terephthalate). They are usually used for the same type of things as PET, but in some cases these perform better. For polystyrene at a glance, click here! Polystyrene is an inexpensive and hard plastic, and probably only polyethylene is more common in your everyday life. The outside housing of the computer you are using now is probably made of polystyrene. Model cars and airplanes are made from polystyrene, and it also is made in the form of foam packaging and insulation (Styrofoam TM is one brand of polystyrene foam). Clear plastic drinking cups are made of polystyrene. So are a lot of the
13 Food Packaging Materials molded parts on the inside of your car, like the radio knobs. Polystyrene is also used in toys, and the housings of things like hairdryers, computers, and kitchen appliances. Polystyrene is a vinyl polymer. Structurally, it is a long hydrocarbon chain, with a phenyl group attached to every other carbon atom. Polystyrene is produced by free radical vinyl polymerization, from the monomer styrene. This is a better picture of what the monomer styrene looks like: Go ahead, play with it! Polystyrene is also a component of a type of hard rubber called poly(styrene-butadiene- styrene), or SBS rubber. SBS rubber is a thermoplastic elastomer. The Polystyrene of the Future There's a new kind of polystyrene out there, called syndiotactic polystyrene. It's different because the phenyl groups on the polymer chain are attached to alternating sides of the polymer backbone chain. "Normal" or atactic polystyrene has no order with regard to the side of the chain on which the phenyl groups are attached.
14 Food Packaging Materials You can see the new syndiotactic polystyrene alongside the old atactic polystyrene in 3-D by clicking here. The new syndiotactic polystyrene is crystalline, and melts at 270 oC. But it's a lot more expensive! Syndiotactic polystyrene is made by metallocene catalysis polymerization. What would happen if we were to take some styrene monomer, and polymerize it free radically, but let's say we put some polybutadiene rubber in the mix. Take a look at polybutadiene, and you'll see that it has double bonds in it that can polymerize. We end up with the polybutadiene copolymerizing with the styrene monomer, to get a type of copolymer called a graft copolymer. This is a polymer with polymer chains growing out of it, and which are a different kind of polymer than the backbone chain. In this case, it's a polystyrene chain with chains of polybutadiene growing out of it.
15 Food Packaging Materials These rubbery chains hanging off of the backbone chain do some good things for polystyrene. Polybutadiene and polystyrene homopolymers don't mix, mind you. So the polybutadiene branches try as best they can to phase separate, and form little globs, like you see in the picture below. But these little globs are always going to be tied to the polystyrene phase. So they have an effect on that polystyrene. They act to absorb energy when the polymer gets hit with something. They give the polymer a resilience that normal polystyrene doesn't have. This makes it stronger, not as brittle, and capable of taking harder impacts without breaking than regular polystyrene. This material is called high- impact polystyrene, or HIPS for short.
16 Food Packaging Materials I'll let you in on a little secret. Not all the chains in HIPS are branched like this. There are a lot chains of plain polystyrene and plain polybutadiene mixed in there, too. This makes HIPS something we call and immiscible blend of polystyrene and polybutadiene. But it is the grafted polystyrene-polybutadiene molecules that make the whole system work by binding the two phases (the polystyrene phase and the polybutadiene phase) together. For poly(vinyl chloride) at a glance, click here! Poly(vinyl chloride) is the plastic known at the hardware store as PVC. This is the PVC from which pipes are made, and PVC pipe is everywhere. The plumbing in your house is probably PVC pipe, unless it's an older house. PVC pipe is what rural high schools with small budgets use to make goal posts for their football fields. But there's more to PVC than just pipe. The "vinyl" siding used on houses is made of poly(vinyl chloride). Inside the house, PVC is used to make linoleum for the floor. In the seventies, PVC was often used to make vinyl car tops. PVC is useful because it resists two things that hate each other: fire and water. Because of its water resistance it is used to make raincoats and shower curtains, and of course, water pipes. It has flame resistance, too, because it contains chlorine. When you try to burn PVC, chlorine atoms are released, and chlorine atoms inhibit combustion. Structurally, PVC is a vinyl polymer. (well, duh!) It is similar to polyethylene, but on every other carbon in the backbone chain, one of the hydrogen atoms is replaced with a chlorine atom. It is produced by the free radical polymerization of vinyl chloride. And here, my friends, is that monomer, vinyl chloride:
17 Food Packaging Materials PVC was one of those odd discoveries that actually had to be made twice. It seems around a hundred years ago, a few German entrepreneurs decided they were going to make loads of cash lighting people's homes with lamps fueled by acetylene gas. Wouldn't you know it, right about the time they had produced tons of acetylene to sell to everyone who was going to buy their lamps, new efficient electric generators were developed which made the price of electric lighting drop so low that the acetylene lamp business was finished. That left a lot of acetylene laying around. So in 1912 one German chemist, Fritz Klatte decided to try to do something with it, and reacted some acetylene with hydrochloric acid (HCl). Now this reaction will produce vinyl chloride, but at that time no one knew what to do with it, so he put it on the shelf, where it polymerized over time. Not knowing what to do with the PVC he had just invented, he told his bosses at his company, Greisheim Electron, who had the material patented in Germany. They never figured out a use for PVC, and in 1925 their patent expired. Wouldn't you know it, in 1926 the very next year, and American chemist, Waldo Semon was working at B.F. Goodrich when he independently invented PVC. But unlike the earlier chemists, it dawned on him that this new material would make a perfect shower curtain. He and his bosses at B.F. Goodrich patented PVC in the United States (Klatte's bosses apparently never filed for a patent outside Germany). Tons of new uses for this wonderful waterproof material followed, and PVC was a smash hit the second time around. For Nylon 6,6 at a glance, click here! For Nylon 6 at a glance, click here! Nylons are one of the most common polymers used as a fiber. Nylon is found in clothing all the time, but also in other places, in the form of a thermoplastic. Nylon's first real success came with its use in women's stockings, in about 1940. They were a big hit, but they became hard to get, because the next year the United States entered World War II, and nylon was needed to make war materials, like parachutes and ropes. But before stockings or parachutes,
18 Food Packaging Materials the very first nylon product was a toothbrush with nylon bristles. Nylons are also called polyamides, because of the characteristic amide groups in the backbone chain. Proteins, such as the silk nylon was made to replace, are also polyamides. These amide groups are very polar, and can hydrogen bond with each other. Because of this, and because the nylon backbone is so regular and symmetrical, nylons are often crystalline, and make very good fibers. The nylon in the pictures on this page is called nylon 6,6, because each repeat unit of the polymer chain has two stretches of carbon atoms, each being six carbon atoms long. Other nylons can have different numbers of carbon atoms in these stretches. Nylons can be made from diacid chlorides and diamines. Nylon 6,6 is made from the monomers adipoyl chloride and hexamethylene diamine. This is one way of making nylon 6,6 in the laboratory. But in a nylon plant, it's usually made by reacting adipic acid with hexamethylene diamine:
19 Food Packaging Materials If you want to know how this works, click here. Another kind of nylon is nylon 6. It's a lot like nylon 6,6 except that it only has one kind of carbon chain, which is six atoms long. It's made by a ring opening polymerization form the monomer caprolactam. Click here to find out more about this polymerization. Nylon 6 doesn't behave much differently from nylon 6,6. The only reason both are made is because DuPont patented nylon 6,6, so other companies had to invent nylon 6 in order to get in on the nylon business. For Poly(methyl methacrylate) at a glance, click here! Poly(methyl methacrylate), which lazy scientists call PMMA, is a clear plastic, used as a shatterproof replacement for glass. The barrier at the ice rink which keeps hockey pucks from flying in the faces of fans is made of PMMA. The chemical company Rohm and Haas makes
20 Food Packaging Materials windows out of it and calls it Plexiglas. Ineos Acrylics also makes it and calls it Lucite. Lucite is used to make the surfaces of hot tubs, sinks, and the ever popular one piece bathtub and shower units, among other things. When it comes to making windows, PMMA has another advantage over glass. PMMA is more transparent than glass. When glass windows are made too thick, they become difficult to see through. But PMMA windows can be made as much as 13 inches (33 cm) thick, and they're still perfectly transparent. This makes PMMA a wonderful material for making large aquariums, whose windows must be thick in order to contain the high pressure millions of gallons of water. In fact, the largest single window in the world, an observation window at California's Monterrey Bay Aquarium, is made of one big piece of PMMA which is 54 feet long, 18 feet high, and 13 inches thick (16.6 m long, 5.5 m high, and 33 cm thick). PMMA is also found in paint. The painting on your right, Acrylic Elf was painted by Pete Halverson with acrylic paints. Acrylic "latex" paints often contain PMMA suspended in water. PMMA doesn't dissolve in water, so dispersing PMMA in water requires we use another polymer to make water and PMMA compatible with each other. To see how we do this, go visit the poly(vinyl acetate) page. But PMMA is more than just plastic and paint. Often lubricating oils and hydraulic fluids tend to get really viscous and even gummy when they get really cold. This is a real pain when you're trying to operate heavy equipment in really cold weather. But when a little bit PMMA is dissolved in these oils and fluids, they don't get viscous in the cold, and machines can be operated down to -100 oC (-150 oF), that is, presuming the rest of the machine can take that kind of cold! PMMA is a vinyl polymer, made by free radical vinyl polymerization from the monomer methyl methacrylate.